Method and composition for suppressing the nitrification of ammonium nitrogen in soil

ABSTRACT

A method for suppressing the nitrification of ammonium nitrogen in soil comprising treating the soil in a plant growing area with a sulfanilamide derivative and a composition therefore.

United States Patent [191 Goya et al.

[451 Jan. 9,1973

[54] METHOD AND COMPOSITION FOR SUPPRESSING THE NITRIFICATION OFAMMONIUM NITROGEN IN SOIL 751 was; anishi; Kenichi Sayvatari, both ofNakatsu; Akira Hirose, Totsuka-ku, Yokohama; Tetsuichi Shinozawa, IChigasaki, all of Japan [73] Assignees: Mitsui-Ioatsu ChemicalsIncorporated, Tokyo; Yoshidomi Pharmaceutical Industries, Osaki, Osaka,Pref., Japan [22] Filed: July 12, 1968 [21] Appl. No.: 744,291

[30] Foreign Application Priority Data July 26, 1967 Japan ..42/47629Dec. 29, 1967 Japan ..42/84878 April 15, 1968 Japan ..43/22046 [52]U.S.C1. ..71/1,71/27, 71/103 [51] Int. Cl. ..C05g 3/08 [58] Field ofSearch ..71/1, 11, 27,103;260/397.7

[56] References Cited UNITED STATES PATENTS 2,238,973 4/1971 Climenko..260/397.7 X 3,009,805 11/1961- 3,011,884 12/1961 3,047,377 7/19623,050,380 8/1962 3,050,381 8/1962 3,050,382 8/1962 3,135,594 6/19643,235,558 2/1966 3,284,188 11/1966 Amegasa et a1. ..71/27 X 3,367,9492/1968 Soyer ..71/103 3,471,436 10/1969 Collins ..260/397.7 3,482,95712/1969 Ueno et a1 ..71/1 2,679,453 5/1954 Brett ..71/94 3,009,80411/1961 Goring ....7l/1 3,011,886 12/1961 Goring ....71/1 3,033,6685/1962 Watkins ....71/1 3,003,825 11/1962 Weil 71/126 3,093,472 6/1963Homeyer et al.. 71/126 3,108,927 10/1963 Pyne .71/122 3,173,919 3/1965Johnston et a1... 71/94 X 3,338,903 8/1967 Harrison ..71/1 3,338,9398/1967 Harrison 71/1 X 3,526,494 9/1970 Toyoda et a1 ..71/30 3,573,0283/1971 Ueno et a1. ..71/1 X FOREIGN PATENTS OR APPLICATIONS 273,7199/1962 Australia ..71/103 275,394 3/1963 Australia ..71/103 734,4774/1966 Canada ..260/397.7 1,516,527 3/1967 France ..260/397.7 39/316661964 7 Japan ..7l/103 39/18852 1964 Japan ..71/103 OTHER PUBLICATIONSGranapathi, Proc. Ind. Asad. Sci., 13A, 1941 pp.386-389 Adams et a1.,Jacs Vol. 61, Sept. 1939, pp. 2342-2349 Dewing et a1., U. Chem. Soc.1942, pp. 239-244 Primary ExaminerReuben Friedman AssistantExaminerRichard Barnes Attorney-Christen & Sabol [57] ABSTRACT A methodfor suppressing the nitrification of ammonium nitrogen in soilcomprising treating the soil in a plant growing area with asulfanilamide derivative and a composition therefore.

10 Claims, No Drawings METHOD AND COMPOSITION FOR SUPPRESSING THENITRIFICATION OF AMMONIUM NITROGEN IN SOIL This invention relates to amethod for suppressing the nitrification of ammonium nitrogen in soiland a composition therefore.

Since most plants obtain the greater part or all of nitrogenrequirements from the soil, it is one of the most important agriculturalproblems to provide nutrient nitrogen in soil for the growth of plants.Nitrogen in soil is present in the three forms of organic nitrogen,ammonium nitrogen and nitrate nitrogen. Among them, ammonium nitrogenand nitrate nitrogen are well absorbed from soil and utilized by plants.In order to be available to the plants, the organic nitrogen must beconverted to ammonia or ammonium salts by soil bacteria. This conversionoccurs very quickly in the case of such organic reduced nitrogenfertilizer as urea, but very slowly in the case of other organicnitrogen compounds.

The ammonium nitrogen in soil is derived from bacterial conversion oforganic nitrogen, or from applied reduced nitrogen fertilizers such asanhydrous ammonia, aqueous ammonia, ammonium sulfate, ammonium nitrateand ammonium phosphate. The ammonium nitrogen in soil is quicklyoxidized to nitrate nitrogen by soil bacteria. (This process is known asnitrification.) The ammonium nitrogen is strongly adsorbed by soil whichis a kind of cation exchanger and is not leached by rainfall orirrigation. However, the nitrate nitrogen which is an anion is notadsorbed by soil and is rapidly leached by rainfall or irrigation.Further, the nitrate nitrogen is reduced to nitrogen gas by soilbacteria. (This process is known as denitrification.) The nitratenitrogen is so rapidly lost from soil as described above that rate ofits utilization by plants is very low. Therefore, in order to preventthe loss of nitrogen from soil and to improve the rate of utilization ofnitrogen by plants, it is necessary to suppress the nitrification ofammonium nitrogen by soil bacteria.

An object of the present invention is to provide an improved method ofpreventing the loss of soil nitrogen. v

Another object of the present invention is to provide an improved methodof suppressing the nitrification of ammonium nitrogen in soil.

A further object of the present invention is to provide a newcomposition to be employed in the method of the present invention.

The subject matter of the present invention is a method of suppressingthe nitrification of ammonium nitrogen in soil comprising treating thesoil in a plant growing area with a sulfanilamide derivative selectedfrom the group consisting of( l the compounds having the formula NH...N@ so.tli m.

I l. x

wherein X is H, Na, K or BCa, Y is CN, CONHR or CSNHR (R is H or analkyl radical having one to four carbons) and N is O or I, (2) thecompounds derived by substituting N of the compounds (1) withmonocarboxylic acids or dicarboxylic acids, and (3) the compoundsderived by substituting N of the compounds having the formula:

with dicarboxylic acids wherein X represents H,

T and each of R, and R in x is H, Cl, Br, cH,,

-OCH SCl-l or NH The above-mentioned wherein R is acyl radical and R isorganic radical to which carboxyl radicals are bonded in dicarboxylicacid.

The above-mentioned compounds (3) are wherein R is organic radical towhich carboxyl radicals are bonded in dicarboxylic acid.

Examples of such compounds include the following: sulfanilythiourea,N-sulfanilyl-N-methylthiourea, N-acetylsulfanilyl-N'-methylthiourea,(N-succinylsulfanilyl)thiourea, acetylsulfanilylcyanamide sodium salt,N-sulfanilyl-N"carbamoylguanidine,

guanidine), maleimidobenzene-N-ethylcarbamoylsulfonamide,sulfanilylurea,

acetylsulfanilylurea,

N-(n-propionylsulfanilyl)-N'-n-propylurea calcium salt,

N-(benzoylsulfanilyl)-N'-isopropylthiocarbamoylguanidine,

acetylsulfanilyldicyandiamide,

N-oxalylsulfanilamide,

2-(N-succinylsulfanilamido)thiazole,

2-(N-malonylsulfanilamido)pyrimidine,

N,Na:-adipyldi(sulfanilylguanidine),

N,Na:-succinyldi(sulfathiazole),

2-(4'-succinimidobenzenesulfonamido)thiazole, and

2-(4'-phthalimidobenzenesulfonamido)pyridine.

By the method of the present invention, the conversion of ammoniumnitrogen in soil to nitrate nitrogen is inhibited and ammonium nitrogencan be prevented from being rapidly lost from soil. This inhibitingaction lasts for a long time. The ammonium nitrogen in this case may bederived from applied fertilizer containing ammonium nitrogen, forexample, ammonia or ammonium salts, or may be formed by conversion of anorganic nitrogen constituent in soil or by the conversion of organicfertilizer applied to soil.

In treating soil with the aforementioned sulfanilamide derivative, it ispreferable to impregnate soil below the soil surface in a plant growingarea with this compound so that the concentration of the compound in thesoil is about 1 to 100 parts by weight, specifically about 1 to 30 partsby weight per million parts by weight of the soil. It is preferable thatthe amount of application of the aforementioned sulfanilamide derivativeis made at least 5 grams per 1 are of the plant growing area.

The aforementioned sulfanilamide derivative may be distributed on aplant growing area prior to, simultaneously with or subsequent to theapplication of a nitrogen fertilizer. Further, when the soil is treatedwith the aforementioned sulfanilamide derivative after the harvest ofcrops, ammonium nitrogen produced from organic substances in the soilcan be preserved for the next growing season. And it is also possible toprevent in the green house the generation of the phytotoxic nitrogendioxide gas from the soil in the plant growing area by treating theplant growing area with the aforementioned sulfanilamide derivative.

In treating a plant growing area with the aforementioned sulfanilamidederivative, this compound may be used as mixed with a soil treatingadjuvant including water, petroleum distillates or other organicsolvent, surface active agent, fine powdered inert solid and nitrogenfertilizer.

The concentration of the aforementioned sulfanilamide derivative in suchcomposition is not critical but can be any amount below percent ofcomposition. Talc, chalk, gypsum, vermiculite, bentonite or diatomaceousearth can be used for the inert solid carrier.

A composition comprising the aforementioned sulfanilamide derivative anda fertilizer is most desirable in working the method of the presentinvention. This composition is produced by dispersing the aforementionedsulfanilamide derivative in a reduced nitrogen fertilizer such asammonia, ammonium salts or urea. Further, this composition may contain aphosphate and/or potassium salt. The reduced nitrogen fertilizer may beeither solid or liquid.

It is preferable that the aforementioned sulfanilamide derivative inthis fertilizer composition is at least 0.5 percent by weight based onthe weight of nitrogen present as reduced nitrogen in the fertilizer. Indispersing the sulfanilamide derivative in a reduced nitrogenfertilizer, it may be mechanically mixed with the fertilizer, or may besprayed on the surfaces of the fertilizer in the form or organic solventsolution such as acetone or ethanol solution, or may be melted with afertilizer of a comparatively low melting point such as urea to mix theaforementioned sulfanilamide derivative with the fertilizer.

In working the method of the present invention, soil can be treated withthe aforementioned sulfanilamide derivative or the compositionscontaining the same by any convenient methods. For example, theaforementioned sulfanilamide derivative or the compositions containingthe same may be mechanically mixed with the soil or may be distributedon the surface of the soil; applied to the surface of soil andthereafter dragged or disced into the soil to a desired depth;transported into the soil with a liquid carrier by injection, sprayingor irrigation. Further, the fertilizer compositions including theaforementioned sulfanilamide derivative can be applied in the samemanner as of applying an conventional fertilizer.

The following examples explain the present invention but are notconstrued as limiting. The parts therein are by weight.

EXAMPLE 1 ding 0.05 part of sulfanilylthiourea to 33 parts of urea anduniformly mixing them, a mixture (II) obtained by adding 0.5 parts ofsulfanilylthiourea to 33 parts of urea and uniformly mixing them and amixture (III) obtained by adding 5 parts of sulfanilylthiourea to 33parts of urea and uniformly mixing them. 50g. of soil were uniformlymixed with each of 33mg. of the mixture (l), 33.5mg. of the mixture (II)and 38mg. of the mixture (Ill). Each of the resulting mixtures contained15mg. of nitrogen per 50g. of the soil. The concentration ofsulfanilylthiourea in the soil was lppm, l0ppm and IOOppm respectively.Each of said mixtures was put into a conical flask of a capacity of c.c.Water was added thereto so that the water content in the soil was 60percent of the maximum water capacity. The flask was plugged withcotton. The contents were incubated at 28C. for 20 days. After thecompletion of the incubation, the nitrogen in the soil was analyzed inrespective forms. Thus the results in Table l were obtained.

The same experiments as described above were carried out on thesulfanilamide derivatives described in Table 1 and also, for comparison,on sodium pentachlorophenate known as a nitrification suppressing agent.The data are mean values of the duplication.

Further, for comparison, there are shown the ana1ysis values of nitrogenin the respective forms in case soil alone and 50g. of soil with theaddition of 33mg. of urea were incubated in the same manner as in theabove described experiment.

TABLE 1 N in mg./50g. of soil Forms of Concentration of the Compoundsnitrogen compounds in soil 1 ppm ppm 100 ppm Sulfanilylthiourea NH -N4.6 12.5 13.7

No -N l 1.1 3.2 2.1 N-Sulfani1y1-N- methylthiourea Nl-l -N 5.2 8.9 14.1

NO N 9.7 6.2 1.0 N-Acetylsulfani1y1-N'- methylthiourea NH -N 3.9 1 1.0 11.1

NO -N l 1.0 4.1 4.0 (N-Succiny1sulfanilyl) thiourea NH -N 6.6 13.1 14.0

NO N 8.8 2.0 1.0 Acetylsulfanilylcyanamide sodium salt NH -N 5.6 11.913.1

No -N 9.2 3.2 1.9 N-sulfanilyl-N" carbamoylguanidine NH -N 4.4 10.1 12.5

No -N 10.6 5.0 2.0 N,Na:-Phthalyldi( N- sulfanilyl -N'-methylcarbamoylguanidine) NO -N 1 1.0 5.8 4.8 Maleimidobenzene-N-ethylcarbamoylsulfonamide NH -N 3.5 8.1 l 1. l

No -N 1 1.9 6.8 4.0 Sulfanilylurea NH -N 5.2 9.9 10.1

NO -N 9.9 5.4 4.8 Acetylsulfanilylurea NH -N 3.7 12.2 15.0

NO -N 1 1.0 2.3 0.4 N-(npropionylsulfonily1)- N'-npropy1urea calciumsalt NH -,-N 3.0 7.9 9.6 NO -N 12.1 7.2 5.6 N-( BenwylsulfanilylN'-isopropylthioearbumoylguunidinc NH -N 3.5 8.8 10.0

No -N 11.9 6.3 5.1 Acetylsulfanilyl dicyandiamide NH -N 4.0 6.8 8.8 No-N l 1.1 8.2 6.7 N-Oxalylsu1fanilamide NH N 3.2 7.7 9.9 NO -N 12.0 7.65.5 2-( N- succinylsulfanilamido) thiazolcNH -N 4.5 12.6 13.6

o -N 11.1 3.2 2.1 2-( N- Malonylsulfanilamido) pyrimidine NOS-N 5.5 6.610.1

NO -N 9.7 8.7 4.8 N,Na.-'Adipyldi(sulfani1ylguanidinc) NH N 1.2 7.0 8.8NO -N 14.0 7.9 6.6 N,Na:-Succinyldi(sulfathiazole) NH -N 2.1 10.6 14.9

No -N 13.4 5. 1 0.7 2-(4- Succinimidobenzene sulfonamido) thiazole NH -N5.5 12.1 14.4

No -N 10.1 3.4 1.1 2-( 4'- Phthalimidobenzenc sulfonamido) pyridine NH-N 4.8 7.6 13.1

No -N 10.1 7.5 2.2 Sodium pentachlorophenate NHa-N 1.0 4.6 7.7

NO -N 14.8 1 1. 1 8. 1 Urea alone Nl-l -N 0.4

NO -N 15.0 Soil alone NH -N 0.2 NO -N 0.3

From the data of Table 1 it is evident that the sulfanilamidederivatives used in the present invention are excellent in thenitrification suppressing activity.

EXAMPLE 2 A dust composition was prepared by mixing 5 parts ofsulfanilylthiourea and 95 parts of talc and then grinding the resultingmixture. 6kg. of this dust composition were distributed on the soilsurface of 10 ares of a plant growing area and plowed into the soil.Then 20kg. of urea were applied.

EXAMPLE 3 A fertilizer composition was prepared by spraying 0.75 part of2-(4-succinimidobenzene sulfonamido)thiazole dissolved in ethanol onto agranular compound fertilizer containing 18% of N, 18% of P 0 and 18% ofK 0 while being rolled in a rotary cylinder and then drying theresulting mixture. Twenty kg. of this fertilizer composition wereapplied to 10 ares of a plant growing area.

EXAMPLE 4 A liquid composition was prepared by mixing 0.5 part of sodiumsalt of acetylsulfanilylcyanamide with 100 parts of aqueous ureasolution containing 50 parts of urea. Thirty kg. of this liquidcomposition were distributed on the soil surface of 10 ares of a plantgrowing area.

EXAMPLE 5 A wettable powder was prepared by mixing parts ofacetylsulfanilylurea, 35 parts of clay and 5 parts of sodiumdodecylbenzenesulfonate as dispersing agent and then grinding theresulting mixture. Three hundred and fifty gr. of this wettable powderwere dispersed in 100 1. of water and sprayed on the soil surface of 10ares of a plant growing area. Then 15kg. of urea were applied.

EXAMPLE 6 An emulsifiable concentrate was prepared by mixing 20 parts of2-(N"-succinylsulfanilamido )thiazole, parts of xylene and 10 parts ofEmanone l 112 (trade name) as emulsifying agent. 1kg. of thisemulsifiable concentrate was mixed with l. of water and sprayed on thesoil surface of 10 ares of a plant growing area a half day after theapplication of 15kg. of urea.

In this invention, the expression reduced nitrogen fertilizers" meansfertilizers containing nitrogen in the 7N-sulfanilyl-N-carbamoylguanidine, (N-succinylsulfanilyl)thiourea,2-(N-succinylsulfanilamido)thiazole and2(4-succinimidobenzenesulfonamido)thiazole.

2. A method as claimed in claim 1 wherein said sulfanilamide derivativeis N-sulfanilyl-N-carbamoyl guanidine.

3. A method as claimed in claim 1 wherein said sulfanilamide derivativeis (N -succinylsulfanilyl)thioutea.

4. A method as claimed in claim 1 wherein said sulfanilamide derivativeis 2-(N -succinylsulfanilamido)thiazole.

5. A method as claimed in claim 1 wherein said sulfanilamide derivativeis 2-(4'-succinimidobenzenesulfonamido) thiazole.

6. A method for suppressing the nitrification of ammonium nitrogentherefrom comprising impregnating the soil below the soil surface in aplant growing area in concentration sufficient to suppress thenitrification with a sulfanilamide derivative selected from the groupconsisting of N-sulfanilyl-N'-carbamoylguanidine, (N succinylsulfanilyl)thiourea, 2-(N -succinylsulfanilamido)thiazole and2(4succinimidobenzenesulfonamido)thiazole, said concentration being fromabout 1 to 100 parts by weight per million parts by weight of soil.

7. A method for suppressing the nitrification of ammonium nitrogenpresent in soil and preventing rapid loss of ammonium nitrogen therefromcomprising impregnating the soil below the soil surface in a plantgrowing area in concentration sufficient to suppress the nitrificationwith a composition comprising a sulfanilamide derivative in mixture witha soil treating adjuvant, said sulfanilamide derivative being selectedfrom the group consisting of N-sulfanilyl-N carbamoylguanidine(N-succinylsulfanilyl)thiourea, 2-(N-succinylsulfanilarnido) thiazoleand 2-(4'-succinimidobenzenesulfonamido )thiazole, said concentrationbeing from about i to parts by weight per million parts by weight ofsoil.

8. A method as claimed in claim 7 wherein said adjuvant is a reducednitrogen fertilizer selected from the group consisting of ammonia,ammonium salts and urea.

9. A fertilizer composition comprising a reduced nitrogen fertilizer assource of ammonium nitrogen and a sulfanilamide derivative selected fromthe group consisting of sulfanilylurea, sulfanilylthiourea,N-sulfanilyl- N'-carbamoylguanidine, (N -succinylsulfanilyl)thiourea,2-(N-succinylsulfanilamido)thiazole and 2-(4-succinimidobenzenesulfonamido)thiazole.

10. A fertilizer composition as claimed in claim 9 wherein said reducednitrogen fertilizer is a member selected from the group consisting ofammonia, ammonium salts and urea and wherein said sulfanilamidederivative is present in a concentration of at least 0.5 per cent byweight based on the weight of the reduced nitrogen in said reducednitrogen fertilizer.

2. A method as claimed in claim 1 wherein said sulfanilamide derivativeis N-sulfanilyl-N''-carbamoyl guanidine.
 3. A method as claimed in claim1 wherein said sulfanilamide derivative is(N4-succinylsulfanilyl)thiourea.
 4. A method as claimed in claim 1wherein said sulfanilamide derivative is2-(N4-succinylsulfanilamido)thiazole.
 5. A method as claimed in claim 1wherein said sulfanilamide derivative is2-(4''-succinimidobenzenesulfonamido) thiazole.
 6. A method forsuppressing the nitrification of ammonium nitrogen therefrom comprisingimpregnating the soil below the soil surface in a plant growing area inconcentration sufficient to suppress the nitrification with asulfanilamide derivative selected from the group consisting ofN-sulfanilyl-N''-carbamoylguanidine, (N4-succinylsulfanilyl) thiourea,2-(N4-succinylsulfanilamido)thiazole and2-(4''-succinimidobenzenesulfonamido)thiazole, said concentration beingfrom about 1 to 100 parts by weight per million parts by weight of soil.7. A method for suppressing the nitrification of ammonium nitrogenpresent in soil and preventing rapid loss of ammonium nitrogen therefromcomprising impregnating the soil below the soil surface in a plantgrowing area in concentration sufficient to suppress the nitrificationwith a composition comprising a sulfanilamide derivative in mixture witha soil treating adjuvant, said sulfanilamide derivative being selectedfrom the group consisting of N-sulfanilyl-N''-carbamoylguanidine(N4-succinylsulfanilyl)thiourea, 2-(N4-succinylsulfanilamido) thiazoleand 2-(4''-succinimidobenzenesulfonamido)thiazole, said concentrationbeing from about 1 to 100 parts by weight per million parts by weight ofsoil.
 8. A method as claimed in claim 7 wherein said adjuvant is areduced nitrogen fertilizer selected from the group consisting ofammonia, ammonium salts and urea.
 9. A fertilizer composition comprisinga reduced nitrogen fertilizer as source of ammonium nitrogen and asulfanilamide derivative selected from the group consisting ofsulfanilylurea, sulfanilylthiourea, N-sulfanilyl-N''-carbamoylguanidine,(N4-succinylsulfanilyl)thiourea, 2-(N4-succinylsulfanilamido)thiazoleand 2-(4''-succinimidobenzenesulfonamido)thiazole.
 10. A fertilizercomposition as claimed in claim 9 wherein said reduced nitrogenfertilizer is a member selected from the group consisting of ammonia,ammonium salts and urea and wherein said sulfanilamide derivative ispresent in a concentration of at least 0.5 per cent by weight based onthe weight of the reduced nitrogen in said reduced nitrogen fertilizer.